3.4-dioxyphenylglyoxims and process of preparing same.



UNITED STATES PATENT OFFICE.

ERNST GBETHER, OF DETROIT, MICHIGAN, ASSIGNOR, BY MESNE ASSIGNMENTS, TO

ADAM BETZING, OF DETROIT, MICHIGAN.

3.4-DIOXYPHENYLGLYOXIMS AND PROCESS OF PREPARING SAMEV Specification of Letters Patent.

Patented Jan. 28, 1913.

No Drawing Application filed July 16,1906, Serial No. 326.300. Renewed'Januax-y 17, 1812. Serial No. 671,565.

formula (ICON-halogen wherein X represents either an alkyl or a hydrogen atom with hydroxylamin-preferably with an excess thereof and with the application of heat-new products are obtained the chemical formula of which may be given as .in which the dioxyphenyl group is attached to a carbon atom of the glyoxim nucleus. These new products serve as the primary source for the production of valuable therapeutic compounds which possess blood raising properties as will be found more fully described in a concurrent application Serial No. 326,301.

The following examples more specifically illustrate how the invention may be practised:

1. To produce 3.4-dioxyphenylglyoxiins, 100 g. chloropyrocatecbin (see llzierzgmvski, Ifm-ichtc, Rci'erate Bd. 26, 588 and B11. 27, 1983) are heated to about 70-75 C. for 3 to 4 hours with a solution of H8 g. of hydroxylamin-hydrochlorid and 98 g. calcined sodium carbonate in 560 g. water. The crystallized product is removed fromthe liquor the next day and washed out with a small quantity of water. From the mother liquor the remainder is obtained by extraction with ether. .The productis then purified by le-crystallization from water to which animal charcoal has been added. A further purification of the productcan be obtained by recrystallization from acetone-lligroin or acetic ether plus ligroin. The

,product thus obtained darkens by subjecting it to a temperature of 150 C. and melts an decomposes at about 170 C. without a sharply defined melting point. In its are state it forms small white needles whic in aqueous solution exposed to the air acquires a darker color. With ferric chlorid a diluted aqueous solution gives an intense reen color. The product is slightly solub e in cold water, more so in hotwater, easily soluble in alcohol and almost insoluble in petrol ether. The result of the analysis made of the new compound and the calculated amounts are as follows:

Calculated. Found I. Found II. N 14.14% 13.75% 14.19% 0 48.48% 48.22%

which agrees with the formula o n up 2. If in the foregoing example the chloracetopyrocatechin is replaced by bromacetopyrocatechin (see Berichte Bd. 26 Referate 588) the result will be the same as above with the separation of hydroxylamin hydrobromid.

3. For the production of 3.4-dioxyphenylmethylglyoxim 75 g. chlorpropiopyrocatechin (see llcrichtc, Referate Bd. 26, 588) or the equivalent amount of brompropiopyrocatechiii together with a solution of 110 hydroxylaminhydrochlorid and 73 g. on? cincd sodium carbonate in 420 g. water are heated to about 7075 C. for 3 to 4 hours. The separation and purification is analogous to Example 1.

The dioxims thus obtained form white needles and have the same characteristics in regard to solubility and color reaction as given for the one in Example 1 with a melting point of from 201 to 202 What I claim is:-

1. The herein described process of producing 3.4-dioxyphenylglyoxiins which consists in subjecting the 3.4-dioxyphenylhalogenalkylketones in Watery solution to the action of hydroxylomin-liydrochloritlin; connectiouwith sodium carbonate and under application of heat, and thence isolatin the product from the solution, substantial y as described.

2 As new products the 3.4l-clioxyphenylglyoxims corresponding to the formula fil'lsn-aoal s in Whichtbe oliox benyl group is attached to a carbon atom o the glyozzim nucleus, the

waists same crystallizing in the form of white needles, soluble in water, more so in hot Water anol easily soluble in alcohol, almost insoluble g1 petrol ether, tasteless, and giving an infbnse green color reaction with ferric chloricllin an aqueous solution, said products by. reduction being transformable into substances having blood raising properties.

In testimony whereof I afix my signature in presence of two Witnesses.

3 ERNST GRETHER. 

